PentaFluoroStyrene-based block copolymers controlled self-assembly pattern: A platform paving the way to functional block copolymers

•Diblock copolymers of 2,3,4,5,6-pentafluorostyrene (PFS) and butyl acrylate (BuA) synthesized by nitroxide mediated polymerization (NMP) with a large range of molar compositions and molecular weights.•Nano-phase separation in thin films due to the high immiscibility of both polymeric blocks.•Versatile self-assembly from out-of-the-plane PPFS to PBuA cylinders crossing through lamellar morphology.•Functionalization of the PPFS block by para fluorine-thiol soft organo-catalysed substitution.•Screening the nano-phase separation by matching the solubility parameters of the modified PFS and BuA monomer units.